A mono coil will work in DD switch position no problem. Remember, this switch used to be called the Rx switch and was labelled Normal, and E (enhance) when it first appeared on the GP extreme. The reason for this was because regardless of switch position the Tx was always the same, the left side Transmit winding always did the transmitting. All that changed was what happened on the Receiving side of things.
So with a DD coil:
In Normal/DD
Left winding - Transmits
Right winding - Receives
In Enhance/Mono
Left winding - Transmits
BOTH SIDES - Receive
In Cancel
Left Winding - Transmits
Both sides - Receive, but one side is +(positive) and the other is -(negative)
So, in my view, a DD is only using half the coils diameter, whereas when in Mono mode, its using half the coil for transmitting, and the whole coil for receiving.
Geoff is correct in that on an 11" DD coil, running it in the Mono mode effectively creates an 11x6" mono, but it's actually the Left side of the coil that is most sensitive. Performance wise, it's like a blend of 11" DD and 8" Mono. Not quite as sensitive as an 8" mono, but handles bad ground a lot better.
So this E/Mono position was initially designed with DD coils in mind, but was soon found to also work with Mono coils. Whatever maths/electronic switching was going on to allow the Rx switching to work also had the effect of a slightly smoother threshold when using a straight mono coil. But, I think there is a very slight drop in audio as well, but seems to vary a bit with different coils.
I have found that certain mono coils are a little "brighter" when run in DD, with negligible difference in threshold stability, whereas others are clearly more settled in the Mono position. So definitely pays you to do some testing with your Mono coils and see which positions responds better. Testing on some buried targets before disturbing the ground is the best way, and you will see when you switch from DD to Mono you will usually have to re ground balance.
Results may also vary with different timings.